This invention relates to a stable liquid polyisocyanate composition having an improved freeze stability which contains an NCO group content of 15 to 30% and a monomeric diphenylmethane diisocyanate content of less than 90%. These compositions comprise (A) an allophanate modified MDI having an NCO group content of 16 to 32.5%, (B) a low molecular weight branched aliphatic dihydroxy compound, and (C) an epoxide functional compound in an amount of from 0.01 to 1% by weight, based on the combined weight of (A) and (B). This invention also relates to a process for the preparation of these stable liquid polyisocyanate compositions.
Diisocyanates that are liquid at room temperature have numerous advantages over solid diisocyanates. The most commercially important diisocyanates that are solid at room temperature are 4,4xe2x80x2-diphenyl-methane diisocyanate and 2,4xe2x80x2-diphenylmethane diisocyanate. Numerous patents have issued relating to the liquification of diphenylmethane diisocyanates (MDI).
One common route to liquification of MDI is through carbodiimidizations. Typical of this route are the processes described in, for example, U.S. Pat. Nos. 3,152,162, 3,384,653, 3,449,256, 3,640,966, 3,641,093, 3,701,796, 4,014,935 4,088,665, 4,154,752 and 4,177,205.
The most common technique to liquify MDI is through the reaction with various hydroxyl functional materials. The prior art has described numerous types of liquid isocyanates. These include both (1) reaction products of (i) MDI or modified MDI with (ii) hydroxyl functional materials such as are described in, for example, U.S. Pat. Nos. 3,644,457, 3,883,571, 4,229,347, 4,055,548, 4,102,833, 4,332,742, 4,448,904, 4,490,301, 4,490,302, 4,539,156, 4,539,158, 4,883,909, 4,442,235 and 4,910,333, as well as (2) mixtures of (i) a reaction product of MDI or modified MDI and hydroxyl functional materials, with (ii) MDI, PMDI or modified MDI, such as are described in, for example, U.S. Pat. Nos. 4,031,026, 4,261,852, 4,321,333, 5,240,635 and 5,246,977.
U.S. Pat. No. 3,644,457 discloses organic diisocyanates and specifically, mixtures of organic diisocyanates which are liquid at room temperature. These compositions comprise the reaction product of solid 4,4xe2x80x2- and/or 2,4xe2x80x2-diphenylmethane diisocyanate with a branched aliphatic dihydroxy compound in a molar ratio of 0.1 to 0.3 mol of dihydroxy compound per mol of diisocyanate. Using the disclosed reaction conditions, allophanate formation by reaction of urethane groups with isocyanate groups does not occur in these isocyanate compositions.
U.S. Pat. Nos. 4,115,429 and 4,118,411 disclose low temperature (i.e., as low as xe2x88x925xc2x0 C.) storage stable liquid diphenylmethane diisocyanates. These are produced by reacting diphenylmethane diisocyanates having a specified 2,4xe2x80x2-isomer content with propylene glycol or poly-1,2-propylene ether glycol. High levels of the 2,4xe2x80x2-isomer result in the desirable improved low temperature stability, however, these products exhibit considerably lower reactivity and also property changes in polyurethane elastomers (i.e., lower tensile strength).
Other liquid isocyanates are described in U.S. Pat. Nos. 4,490,300, 4,490,301 and 4,490,302. U.S. Pat. No. 4,490,300 discloses reaction products of MDI with an aliphatic diol having a pendant aromatic group, e.g., 2-methyl-2-phenyl-1,3-propanediol or phenyl-1,2-ethanediol. These liquid isocyanates are disclosed as being stable at room temperature. Other liquid isocyanates which are stable at room temperatures include those which comprise the reaction product of MDI with monoallylether of trimethylolpropane. Liquid isocyanate reaction products are also disclosed by U.S. Pat. No. 4,490,302. These comprise the reaction products of MDI with mixtures of monoalcohols, poly-1,2-propylene ether glycols and low molecular weight triols.
U.S. Pat. No. 4,738,991 discloses organic polyisocyanates which are characterized by allophanate linkages. These polyisocyanates are prepared by reacting an organic polyisocyanate and include, 2,4xe2x80x2 and 4,4xe2x80x2-diphenylmethane diisocyanate with poly- or a monohydric alcohol in the presence of an organometallic catalyst. Deactivation of the catalyst is achieved using a compound such as an inorganic acid, organic acid, organic chloroformate or an organic acid chloride.
U.S. Pat. No. 4,866,103 discloses a polyisocyanate composition for use in producing elastomers in a RIM process. This composition is the product of reacting an alcohol or thiol having an average functionality of from about 1.5 to about 4 and an average equivalent weight of at least about 500 with at lest 2 equivalents per hydroxyl and/or thiol equivalent of an organic polyisocyanate including the 4,4xe2x80x2- and the 2,4xe2x80x2-isomers of diphenylmethane diisocyanate. These products are formed under conditions such that at least about 20% of the initially formed urethane or thiourethane groups are converted to allophanate and/or thioallophanate groups.
Other references relating to the preparation of allophanates containing isocyanate include GB Patent 994,890. This reference relates to the reaction of urethane isocyanates with excess diisocyanate either by heat alone or in the presence of a catalyst such as a metal carboxylate, a metal chelate or a tertiary amine, until the isocyanate content is reduced to that which is obtained theoretically when the complete reaction of the urethane groups is achieved.
U.S. Pat. No. 4,160,080 discloses a process for producing allophanate containing aliphatically and/or cycloaliphatically bound isocyanate groups in which compounds containing urethane groups are reacted with polyisocyanates having aliphatic and/or cycloaliphatic isocyanate groups, in the presence of a strong acid. The process is generally conducted at a temperature of from 90xc2x0 C. to 140xc2x0 C. for about 4 to 20 hours.
A method of preparing liquid diphenylmethane diisocyanate is disclosed by Japanese Patent Application No. 1971-99176. These are prepared by reacting diphenylmethane diisocyanate with aliphatic monovalent alcohol.
Novel, liquid diphenylmethane diisocyanates which contain allophanate linkages are also disclosed by U.S. Pat. Nos. 5,319,053 and 5,319,054. The liquid stable products of U.S. Pat. No. 5,319,053 are characterized by an NCO group content of 12 to 32.5%, and comprise the reaction product of an aliphatic alcohol and a specified mixture of isomers of diphenylmethane diisocyanate. This reference also discloses stable liquid MDI prepolymers which comprise the reaction product of the allophanate-modified MDI as described above, with an organic material containing two or more active hydrogen groups. U.S. Pat. No. 5,319,054 describes liquid allophanate modified MDI compositions which are storage stable at 25xc2x0 C. The diphenylmethane diisocyanate has a specific isomer distribution requiring 2 to 60% by weight of 2,4xe2x80x2-diphenylmethane diisocyanate. The disclosed allophanate containing MDI prepolymers, although storage stable at 25xc2x0 C., are substantially lower in reactivity with polyols when compared to stable liquid MDI""s according to the present invention. Polyurethane elastomers prepared from allophanate modified MDI having higher 2,4xe2x80x2-isomer content as described in this reference also result in products with lower hardness and tensile strength.
Allophanate modified diphenylmethane diisocyanate prepolymers are described in U.S. Pat. No. 5,440,003. These products are stable liquids at 25xc2x0 C., and comprise the reaction product of an isomeric mixture of diphenylmethane diisocyanate and an aromatic alcohol such as phenol, with the resultant product being converted to the allophanate having an NCO group content of 12 to 32% by weight.
U.S. Pat. No. 5,663,272 discloses allophanate modified MDI which is a storage stable liquid at 25xc2x0 C. These compositions are prepared by reacting a monoisocyanate and an organic material having at least two hydroxyl groups and a molecular weight of 60 to 6,000 to form a urethane. The urethane is then reacted with an isomeric mixture of MDI to form an isocyanate product having an NCO group content of from 12 to 30%. This allophanate-modified MDI can be further reacted with an organic isocyanate-reactive material to form an allophanate-modified MDI prepolymer containing urethane, urea and/or biuret groups having an NCO group content of 5 to 29%. The use of monofunctional compounds in polyurethane formulations including prepolymers results in chain termination which yields lower molecular weight polyurethanes with inferior physical properties.
Polyisocyanate mixtures which are liquid at temperatures greater than 5xc2x0 C. are disclosed by U.S. Pat. No. 5,610,260. These polyisocyanates have an NCO content of 14.5 to 24% by weight and an allophanate group content of 7.7 to 14.5% by weight. The polyisocyanates described comprise reaction products of 4,4xe2x80x2-diphenylmethane diisocyanate with one or more monohydric alcohols having 4 to 16 carbon atoms at an NCO:OH equivalent ratio of 5:1 to 8.5:1, and a temperature of up to 160xc2x0 C. to form urethane groups, and during or subsequent to urethane formation, converting the urethane groups in the presence of a catalyst to allophanate groups. Allophanate modified liquid MDI products made by this process provide improved low temperature stability, but are much slower in reactivity compared with products of the present invention and result in polyurethane elastomers with considerable lower elasticity (i.e. elongation).
Mixtures of epoxide functional compounds and urethane prepolymers of allophanate-modified diphenylmethane diisocyanates are known and described in, for example, U.S. Pat. 5,783,652. The addition of the epoxide functional compound is described as increasing the reactivity by lowering the acidity of the urethane modified allophanate-modified MDI monomers.
Advantages of the present invention include low temperature stability combined with desirable reactivity comparable to liquid MDI/tripropylene glycol adducts and provision of excellent physical properties (combination of hardness, elongation, and tensile strength) in resulting polyurethane elastomers.
This invention relates to stable liquid polyisocyanate compositions characterized by improved freeze stability. These stable liquid polyisocyanate compositions have an NCO group content of from 15 to 30% (preferably of from 20 to 26%), and have a monomeric diphenylmethane diisocyanate content of less than 90% by weight, preferably of less than 70%. These stable liquid polyisocyanate compositions comprise:
(A) an allophanate-modified MDI having an NCO group content of 16 to 32.5%, and comprising the reaction product of:
(1) diphenylmethane diisocyanate containing from about 0 to about 20% by weight of the 2,4xe2x80x2-isomer, from about 0 to about 2% of the 2,2xe2x80x2-isomer, and the balance being the 4,4xe2x80x2-isomer, and
(2) an aliphatic alcohol;
(B) a low molecular weight branched aliphatic dihydroxy compound (preferably tripropylene glycol), and
(C) an epoxide functional compound in the amount of 0.01 to 1% by weight, based on the combined weight of (A) and (B).
The present invention also relates to a process for the preparation of stable liquid polyisocyanate compositions characterized by improved freeze stability. This process comprises:
(I) reacting
(A) an allophanate-modified MDI having an NCO group content of 16 to 32.5% which comprises the reaction product of (1) diphenylmethane diisocyanate containing from about 0 to about 20% by weight of the 2,4xe2x80x2-isomer, from about 0 to about 2% by weight of the 2,2xe2x80x2-isomer and the balance being the 4,4xe2x80x2-isomer, and (2) an aliphatic alcohol; with
(B) a low molecular weight branched aliphatic dihydroxy compound (preferably tripropylene glycol), thereby forming an allophanate-modified MDI prepolymer; and
(II) adding
(C) an epoxide functional compound to the allophanate-modified prepolymer,
wherein (C) is present in an amount of from 0.01 to 1% by weight, based on the combined weight of (A) and (B).
As used herein with respect to the polyisocyanate compositions of the invention, the term stable means that the polyisocyanate composition has no more than a 1% absolute change in the NCO content and no more than a 10% change in the viscosity when stored at 25xc2x0 C. for 3 months, and the term liquid means that the polyisocyanate composition does not precipitate solids when stored at 25xc2x0 C. for 3 months.
In accordance with the present invention, suitable compositions to be used as component (A) include allophanate-modified MDI having an NCO group content of from 16 to 32.5%, preferably of 21 to 29%.
Suitable (A) allophanate-modified MDI for the present invention comprises the reaction product of:
(1) diphenylmethane diisocyanate containing from about 0 to about 20% by weight of the 2,4xe2x80x2-isomer, from about 0 to about 2% by weight of the 2,2xe2x80x2-isomer and the balance being the 4,4xe2x80x2-isomer; and
(2) an aliphatic alcohol.
The diphenylmethane diisocyanate suitable for component (A)(1) of the present invention has the isomer distribution as set forth above, wherein the sum of the %""s by weight of 2,2xe2x80x2-isomer, 2,4xe2x80x2-isomer and 4,4xe2x80x2-isomer must total 100% by weight of the diphenylmethane diisocyanate (A)(1). It is preferred that the diphenylmethane diisocyanate contains from about 0 to 10% by weight of the 2,4xe2x80x2-isomer, from about 0 to about 1% by weight of the 2,2xe2x80x2-isomer, and the balance being the 4,4xe2x80x2-isomer. Most preferably, the MDI contains from about 0 to 3% by weight of the 2,4xe2x80x2-isomer, from about 0 to 0.2% by weight of the 2,2xe2x80x2-isomer and the balance being the 4,4xe2x80x2-isomer.
Suitable aliphatic alcohols to be used as component (A)(2) can contain about 1 to 36 and preferably 4 to 16 carbon atoms. Illustrative but non-limiting examples of the aliphatic alcohols can be selected from the group consisting of cycloaliphatic alcohols, aliphatic alcohols containing aromatic groups, aliphatic alcohols containing groups that do not react with isocyanates, e.g. ether groups and halogens such as bromine and chlorine. Specific but non-limiting examples of the aliphatic alcohols can be selected from the group consisting of 2-methyl-1-propanol, cetylalcohol, cyclohexanol, 2-methoxyethanol, and 2-bromoethanol. Aliphatic alcohols for the present invention which are more preferred include the branched aliphatic alcohols such as, for example, isobutanol.
The allophanate-modified MDI, i.e., component (A) of this invention, can be prepared by, for example, the process disclosed in U.S. Pat. No. 5,319,053, the disclosure of which is herein incorporated by reference.
Suitable low molecular weight branched aliphatic dihydroxy compounds which are suitable to be used as component (B) of the present invention include, for example, branched aliphatic dihydroxy compounds such as, 2-ethyl hexanediol-(1,3), 2-methylpentane-diol-(2,4), 2,2,4-tri-methylpentanediol-(1,3), 3-methyl-5-ethylheptane diol-(2,4), 2-methyl-2-propanediol-(1,3) or mixtures thereof. It is preferred to use poly-1,2-propylene ether glycols of molecular weight 134 to 700, such as dipropylene glycol, tripropylene glycol or polypropylene glycol or mixtures thereof. Tripropylene glycol is particularly preferred.
Any chemical compound which contains the epoxide (oxirane) functionality is suitable for component (C) in the polyisocyanate compositions of the present invention. The term xe2x80x9cepoxidexe2x80x9d or xe2x80x9cepoxyxe2x80x9d as used herein refers to any organic compound or resin comprising at least one group comprising a three membered oxirane ring. Preferably, two or more oxirane groups are present in the epoxide compound or resin in order to obtain the polyisocyanate compositions with consistent reactivity profiles of the instant invention. The epoxide equivalent weight (EEW) range of suitable epoxides is from about 44 to 400, preferably 100 to 350 and most preferably 150 to 300. Both aliphatic mono- and polyepoxides may be used, and are well known.
It is somewhat less preferred that the epoxy contains an aromatic group due to the tendency of them to cause yellowing as well as their reduced efficacy. Examples of such aromatic group containing polyepoxides include but are not limited to those selected from the group consisting of the polyglycidyl ethers of polyhydric phenols; glycidyl esters of aromatic carboxylic acids; N-glycidylaminoaromatics such as N-glycidylaminobenzene, N,N,Nxe2x80x2,Nxe2x80x2-tetraglycidyl-4,4xe2x80x2-bis-aminophenyl methane, and diglycidylaminobenzene; glycidylaminoglycidyloxy-aromatics such as glycidylaminoglycidyloxybenzene; and mixtures thereof.
The preferred epoxides for use according to the invention are the aliphatic epoxides which do not contain hydroxyl groups.
Suitable for use are C2-C10 aliphatic epoxides such as, for example, ethylene oxide, propylene oxide, 1,2-butene oxide, 2,3-butene oxide (cis and/or trans), isobutylene oxide, 1,2-pentene oxide, 2,3-pentene oxide, cyclopentene oxide, 1,2-hexene oxide, cyclohexene oxide, and the like and mixtures thereof.
Examples of useful aliphatic polyepoxides include but are not limited to those selected from the group consisting of vinyl cyclohexene dioxide; butadiene dioxide; and those containing ether linkages such as triglycidyl isocyanurate, triglycidyl pentaerythritol, tetraglycidyl pentaery-thritol, diglycidylethers of cylcohexane dimethanol and the diglycidylethers of other diols known to those skilled in the art, 1,4-bis(2,3-epoxypropoxy)-benzene; 1,3-bis(2,3-epoxypropoxy)benzene; 4,4xe2x80x2-bis(2,3-epoxypropoxy)-diphenyl ether; 1,8-bis(2,3-epoxypropoxy)octane; 1,4-bis(2,3-epoxypropoxy)cyclohexane; 4,4xe2x80x2-(2-hydroxy-3,4-epoxybutoxy)-diphenyl dimethyl methane; 1,3-bis(4,5-epoxypentoxy)-5-chlorobenzene; 1,4-bis(3,4-epoxybutoxy)-2-chlorocyclohexane; diglycidyl thioether; diglycidyl ether; 1,2,5,6-diepoxyhexane-3; 1,2,5,6-diepoxyhexane; those containing ester groups such as ERL 4221, a product of Union Carbide Corporation, illustrated in U.S. Pat. No. 4,814,103, the disclosure of which is herein incorporated by reference, and mixtures thereof.
Other useful epoxides are listed in, for example, U.S. Pat. No. 3,298,998, the disclosure of which is herein incorporated by reference. These compounds include but are not limited to those selected from the group consisting of bis[p-(2,3-epoxypropoxy)phenyl]cyclohexane; 2,2-bis[p-(2,3-epoxypropoxy)phenyl]norcamphane; 5,5-bis[(2,3-epoxypropoxy)phenyl]hexahydro-4,6-methanoindane; 2,2-bis[4-(2,3-epoxypropoxy)-3-methylphenyl]hexahydro-4,7-methanoindane; and 2-bis[p-2,3-epoxypropoxy)phenyl]-methylene-3-methylnorcamphane; and mixtures thereof. Other usable epoxides are found in, for example, Handbook of Epoxy Resin, Lee and Neville, McGraw-Hill, New York (1967) and U.S. Pat. No. 3,018,262, both of which are herein incorporated by reference.
Also, suitable epoxides for use in the present invention include the epoxidized dimer and trimer fatty acids, which are formed by epoxidizing the products of the polymerization of C18 unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, elaidic acid and the like. The use of a dimer or trimer fatty acid entity furnishes a higher molecular weight epoxide that is less likely to volatilize from the finished articles that the polyisocyanate compositions of the present invention are used to produce. The dimer fatty acid may have an acyclic, monocyclic, or bicyclic structure or comprise a mixture of compounds having different such structures.
Epoxidized mono-, di- and triglycerides prepared by epoxidation of the known unsaturated or partially unsaturated glycerides are preferred. The epoxidized glycerides may be prepared from any of the known fatty acid triglycerides available from natural or synthetic sources. The fatty acid group, which is connected to glycerol by an ester bond is usually a C6-C24 monocarboxylic acid (linear or branched; saturated, monounsaturated, or polyunsaturated). Such fatty acids and their equivalents are readily available at low cost from natural sources such as edible triglycerides. Specific illustrative fatty acids suitable for use include, but are not limited to, eicosanoic (arachidic) acid, heneicosanoic acid, docosanoic (behenic) acid, elaidic acid, tricosanoic acid, tetracosanoic (lignoceric) acid, caprylic acid, pelargonic acid, capric acid, caproic acid, lauric acid, palmitic acid, stearic acid, oleic acid, cetoleic acid, myristic acid, palmitoleic acid, gadoleic acid, erucic acid, rincinoleic acid, linoleic acid, linolenic acid, myristoleic acid, eleostearic acid, arachidonic acid, or mixtures or hydrogenated derivatives of these acids. The fatty acids may be derived synthetically or from natural sources such as triglyceride lipids. Mixtures of fatty acid entities, such as the mixtures of fatty acids typically obtained by hydrolysis (splitting) of a triglyceride are also suitable. These fatty acid triglycerides include, but are not limited to, fats and oils such as tallow, soybean oil, cottonseed oil, coconut oil, palm kernel oil, corn oil, fish oil, lard, butterfat, olive oil, palm oil, peanut oil, safflower seed oil, cocoa butter, sesame seed oil, rapeseed oil, sunflower seed oil, as well as fully or partially hydrogenated derivatives and mixtures of these triglycerides. Epoxidized linseed oil is particularly preferred.
A process for preparing the liquid polyisocyanate compositions of the present invention includes the following steps:
Diphenylmethane diisocyanate is charged to a reactor and heated to about 60xc2x0 C. under agitation. A calculated amount of the chosen aliphatic alcohol containing 1 to 36 carbon atoms is added, followed by the catalytic amounts of zinc acetylacetonate or other suitable catalyst. The reaction mixture is stirred at 90xc2x0 C. until the calculated NCO content is reached (i.e., about 16 to about 32.5% NCO). At this time, a small amount of benzoyl chloride (or other suitable stopper) is added to deactivate the catalyst. The allophanate-modified MDI is subsequently cooled to 60xc2x0 C. and a calculated amount of a branched aliphatic dihydroxy compound is added and reacted with the allophanate-modified MDI until the calculated isocyanate content is reached (i.e., about 15 to about 30% NCO). Before or after cooling to 25xc2x0 C., a small amount of the epoxide functional compound is added (i.e., 0.01 to 1% based on the combined weight of components (A) and (B)). The final isocyanate content, the viscosity, and the freezing point are determined and the product is stored until used in the preparation of a polyurethane.
As used herein, the term xe2x80x9cimproved freeze stabilityxe2x80x9d with respect to the presently claimed isocyanate compositions means that these isocyanate compositions are stable liquids at less than 20xc2x0 C., and preferably at less than 15xc2x0 C. for 30 days or more.
Applicants copending application Ser. No. 09/499,603, now issued U.S. Pat. No. 6,242,556, which is commonly assigned, also describes liquid MDI adducts having improved freeze stability. These compositions comprise a blend of (A) an MDI adduct having an NCO group content of 15 to 30%, and (B) an allophanate-modified MDI having an NCO group content of 12 to 32.5%.
The following examples further illustrate details for the preparation and use of the compositions of this invention. The invention, which is set forth in the foregoing disclosure, is not to be limited either in spirit or scope by these examples. Those skilled in the art will readily understand that known variations of the conditions and processes of the following preparative procedures can be used to prepare these compositions. Unless otherwise noted, all temperatures are degrees Celsius and all parts and percentages are parts by weight and percentages by weight, respectively.